Substituted pyrimidines

ABSTRACT

The invention relates to substituted pyrimidines of the general formula (I)  
                 
         in which n, R 1 , R 2 , R 3  and Z are as defined in the disclosure, to their use as crop treatment agents, in particular as herbicides, and to processes for their preparation.

The invention relates to novel substituted pyrimidines, to a process fortheir preparation and to their use as crop treatment agents, inparticular as herbicides.

It is already known that certain substituted pyrimidines, such as, forexample, the compound5-(3,5-bistrifluoromethylphenyl)-3-[1-(4,5,6-trimethylpyrimid-2-ylthio)-ethyl]-1,2,4-oxadiazole,have herbicidal properties (cf. GB-A-2205101). However, the action ofthese compounds is not entirely satisfactory.

Further substituted pyrimidines, such as, for example, the compounds2-benzylthio-4-chloro-5-methylpyrimidine,4-chloro-2-(2,4-dichlorobenzylthio)-5-methylpyrimidine,4-chloro-2-(2-chlorobenzylthio)-5-methylpyrimidine and4-chloro-2-(4-chlorobenzylthio)-5-methylpyrimidine (cf. J. Org. Chem. 27(1962), 181-185), the compound4,6-dichloro-5-methyl-2-(naphthalen-2-ylmethylthio)pyrimidine (cf.WO-A-95/13267), the compound5-methyl-2-[(1-methyl-5-nitro-1H-imidazol-2-yl)methylthio]pyrimidine(cf. U.S. Pat. No. 3,991,191), and the compounds2-(thien-2-ylmethylsulphonyl)-5-trifluoromethylpyrimidine,2-phenylmethylthio-5-trifluoromethylpyrimidine,2-(thien-2-ylmethylthio)-5-trifluoromethylpyrimidine,2-phenylmethylsulphonyl-5-trifluoromethylpyrimidine and2-(thien-2-ylmethylsulphinyl)-5-trifluoromethylpyrimidine (cf.GB-A-2135992) have been disclosed as potential pharmaceutically activecompounds. However, hitherto nothing has been disclosed relating topossible applications of these compounds in crop protection.

This invention now provides the substituted pyrimidines of the generalformula (I)

in which

-   n represents the number 0, 1 or 2,-   A represents straight-chain or branched alkanediyl having 1 to 6    carbon atoms,-   R¹ represents hydrogen, halogen, optionally halogen- or    C₁-C₄-alkoxy-substituted alkyl having 1 to 6 carbon atoms, or    optionally halogen- or C₁-C₄-alkyl-substituted phenyl,-   R² represents optionally halogen- or C₁-C₄-alkoxy-substituted alkyl    having 1 to 6 carbon atoms, represents optionally halogen- or    C₁-C₄-alkyl-substituted cycloalkyl having 3 to 8 carbon atoms, or    represents optionally halogen- or C₁-C₄-alkyl-substituted    phenyl-C₁-C₄-alkyl, or together with R¹ or together with R³    represents optionally C₁-C₄-alkyl-substituted alkanediyl having 3 to    5 carbon atoms or an optionally halogen- or C₁-C₄-alkyl-substituted    benzo grouping,-   R³ represents hydrogen, halogen, optionally halogen- or    C₁-C₄-alkoxy-substituted alkyl having 1 to 6 carbon atoms, or    optionally halogen- or C₁-C₄-alkyl-substituted phenyl, and-   Z represents in each case optionally substituted phenyl, naphthyl,    pyridinyl, pyrimidinyl, furyl, thienyl, oxazolyl or thiazolyl, where    the substituents possible in each case are selected from the list    below:    -   nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, in        each case optionally cyano-, carboxyl-, carbamoyl-,        thiocarbamoyl-, halogen-, C₁-C₄-alkoxy-, C₁-C₄-alkylthio-,        C₁-C₄-alkylsulphinyl- or C₁-C₄-alkylsulphonyl-substituted alkyl,        alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl,        alkylsulphonyl, alkylamino, alkylaminocarbonyl or        alkylcarbonylamino having in each case 1 to 6 carbon atoms in        the alkyl groups, in each case optionally halogen-substituted        alkylenedioxy having 1 or 2 carbon atoms, dialkylamino,        dialkylaminocarbonyl or dialkylaminosulphonyl having in each        case 1 to 4 carbon atoms in the alkyl groups, in each case        optionally nitro-, cyano-, carboxyl-, carbamoyl-,        thiocarbamoyl-, halogen-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-,        C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,        C₁-C₄-haloalkylthio-, C₁-C₄-alkylsulphinyl-,        C₁-C₄-haloalkylsulphinyl-, C₁-C₄-alkylsulphonyl- or        C₁-C₄-haloalkylsulphonyl-substituted phenyl, phenoxy,        phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,        phenylcarbonylamino, phenyl-C₁-C₄-alkyl, phenyl-C₁-C₄-alkoxy,        phenoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkylthio,        phenyl-C₁-C₄-alkylsulphinyl, phenyl-C₁-C₄-alkylsulphonyl,        phenyl-C₁-C₄-alkylamino.

Saturated or unsaturated hydrocarbon groupings, such as alkyl,alkanediyl, alkenyl or alkynyl are in each case straight-chain orbranched as far as this is possible—including in combination withheteroatoms, such as in alkoxy.

Optionally substituted radicals can be mono- or polysubstituted, and inthe case of polysubstitution, the substituents can be identical ordifferent.

The compounds of the general formula (I) according to the invention maycontain one or more asymmetrically substituted carbon atoms, in whichcases they may be present in different enantiomeric (R- andS-configured) forms or diastereomeric forms. In these cases, theinvention relates both to the use of the different possible individualenantiomeric or stereoisomeric forms of the compounds of the generalformula (I) and of mixtures of these isomeric compounds.

Preferred substituents or ranges of the radicals present in the formulaegiven above and below are defined below.

n preferably represents the number 0, 1 or 2.

A preferably represents straight-chain or branched alkanediyl having 1to 4 carbon atoms.

R¹ preferably represents hydrogen, halogen, optionally halogen- orC₁-C₄-alkoxy-substituted alkyl having 1 to 4 carbon atoms, or optionallyhalogen- or C₁-C₄-alkyl-substituted phenyl.

R² preferably represents optionally halogen- or C₁-C₄-alkoxy-substitutedalkyl having 1 to 5 carbon atoms, represents optionally halogen- orC₁-C₃-alkyl-substituted cycloalkyl having 3 to 7 carbon atoms, orrepresents optionally halogen- or C₁-C₄-alkyl-substitutedphenyl-C₁-C₄-alkyl, or together with R¹ or together with R³ representsoptionally C₁-C₃-alkyl-substituted alkanediyl having 3 to 5 carbon atomsor an optionally halogen- or C₁-C₃-alkyl-substituted benzo grouping.

R³ preferably represents hydrogen, halogen, optionally halogen- orC₁-C₄-alkoxy-substituted alkyl having 1 to 4 carbon atoms, or optionallyhalogen- or C₁-C₄-alkyl-substituted phenyl.

Z preferably represents in each case optionally substituted phenyl,naphthyl, pyridinyl, pyrimidinyl, furyl, thienyl, oxazolyl or thiazolyl,where the substituents possible in each case are preferably selectedfrom the list below:

-   -   nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, in        each case optionally cyano-, carboxyl-, carbamoyl-,        thiocarbamoyl-, halogen-, C₁-C₄-alkoxy-, C₁-C₄-alkylthio-,        C₁-C₄-alkylsulphinyl- or C₁-C₄-alkylsulphonyl-substituted alkyl,        alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl,        alkylsulphonyl, alkylamino, alkylaminocarbonyl or        alkylcarbonylamino having in each case 1 to 5 carbon atoms in        the alkyl groups, in each case optionally halogen-substituted        alkylenedioxy having 1 or 2 carbon atoms, dialkylamino,        dialkylaminocarbonyl or dialkylaminosulphonyl having in each        case 1 to 3 carbon atoms in the alkyl groups, in each case        optionally nitro-, cyano-, carboxyl-, carbamoyl-,        thiocarbamoyl-, halogen-, C₁-C₄-alkyl-, C₁-C₄-haloalkyl-,        C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,        C₁-C₄-haloalkylthio-, C₁-C₄-alkylsulphinyl-,        C₁-C₄-haloalkylsulphinyl-, C₁-C₄-alkylsulphonyl- or        C₁-C₄-haloalkylsulphonyl-substituted phenyl, phenoxy,        phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,        phenylcarbonylamino, phenyl-C₁-C₄-alkyl, phenyl-C₁-C₄-alkoxy,        phenoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkylthio,        phenyl-C₁-C₄-alkylsulphinyl, phenyl-C₁-C₄-alkylsulphonyl,        phenyl-C₁-C₄-alkylamino.

n particularly preferably represents the number 0, 1 or 2.

A particularly preferably represents methylene, ethane-1,1-diyl(ethylidene), ethane-1,2-diyl (dimethylene), propane-1,1-diyl(propylidene), propane-1,2-diyl or propane-1,3-diyl (trimethylene).

R¹ particularly preferably represents hydrogen, fluorine, chlorine,bromine, iodine, represents in each case optionally fluorine-,chlorine-, bromine-, methoxy-, ethoxy-, n- or isopropoxy-substitutedmethyl, ethyl, n- or isopropyl, n-, iso-, s- or t-butyl or optionallyfluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or isopropyl-, n-,iso-, s- or t-butyl-substituted phenyl.

R² particularly preferably represents in each case optionally fluorine-,chlorine-, bromine-, methoxy-, ethoxy-, n- or isopropoxy-substitutedmethyl, ethyl, n- or isopropyl, n-, iso-, s- or t-butyl, represents ineach case optionally fluorine-, chlorine-, methyl- or ethyl-substitutedcyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or represents ineach case optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-or isopropyl, n-, iso-, s- or t-butyl-substituted benzyl or phenylethyl,or together with R¹ or together with R³ represents in each caseoptionally methyl- and/or ethyl-substituted propane-1,3-diyl(trimethylene) or butane-1,4-diyl (tetramethylene) or an optionallyfluorine-, chlorine- or methyl-substituted benzo grouping.

R³ particularly preferably represents hydrogen, fluorine, chlorine,bromine, iodine, in each case optionally fluorine-, chlorine-, bromine-,methoxy-, ethoxy-, n- or isopropoxy-substituted methyl, ethyl, n- orisopropyl, n-, iso-, s- or t-butyl, or optionally fluorine-, chlorine-,bromine-, methyl-, ethyl-, n- or isopropyl-, n-, iso-, s- ort-butyl-substituted phenyl.

Z particularly preferably represents in each case optionally substitutedphenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, thienyl, oxazolyl orthiazolyl, where the substituents possible in each case are particularlypreferably selected from the following list:

-   -   nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine,        chlorine, bromine, iodine, in each case optionally cyano-,        carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-,        methoxy-, ethoxy-, n- or isopropoxy-, methylthio-, ethylthio-,        n- or isopropylthio-, methylsulphinyl-, ethylsulphinyl-,        methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n-        or isopropyl, n-, iso-, s- or t-butyl, methoxy, ethoxy, n- or        isopropoxy, n-, iso-, s- or t-butoxy, methoxycarbonyl,        ethoxycarbonyl, n- or isopropoxycarbonyl, methylthio, ethylthio,        n- or isopropylthio, n-, iso-, s- or t-butylthio,        methylsulphinyl, ethylsulphinyl, n- or isopropylsulphonyl,        methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- or        isopropylamino, n-, iso-, s- or t-butylamino,        methylaminocarbonyl, ethylaminocarbonyl, n- or        isopropylaminocarbonyl, acetylamino, propionylamino, n- or        isobutyroylamino, in each case optionally fluorine- and/or        chlorine-substituted methylenedioxy or ethylenedioxy,        dimethylamino, diethylamino, dimethylaminocarbonyl or        dimethylaminosulphonyl, in each case optionally nitro-, cyano-,        carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-,        bromine-, methyl-, ethyl-, n- or isopropyl-, n-, iso-, s- or        t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or        isopropoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-,        ethylthio-, n- or isopropylthio-, difluoromethylthio-,        trifluoropmethylthio-, methylsulphinyl-, ethylsulphinyl-,        trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl- or        trifluoromethylsulphonyl-substituted phenyl, phenoxy,        phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,        phenylcarbonylamino, benzyl, phenylethyl, phenylmethoxy,        phenylethoxy, phenoxymethyl, phenoxyethyl, phenylmethylthio,        phenylethylthio, phenylmethylsulphinyl, phenylethylsulphinyl,        phenylmethylsulphonyl, phenylethylsulphonyl, phenylmethylamino,        phenylethylamino.

n very particularly preferably represents the number 0, 1 or 2.

A very particularly preferably represents methylene, ethane-1,1-diyl(ethylidene) or ethane-1,2-diyl (dimethylene).

R¹ very particularly preferably represents hydrogen, fluorine, chlorine,bromine, in each case optionally fluorine-, chlorine-, bromine-,methoxy- or ethoxy-substituted methyl, ethyl, n- or isopropyl, oroptionally fluorine-, chlorine-, bromine- or methyl-substituted phenyl.

R² very particularly preferably represents in each case optionallyfluorine-, chlorine-, bromine-, methoxy- or ethoxy-substituted methyl,ethyl, n- or isopropyl, n-, iso- or s-butyl, or represents optionallyfluorine-, chlorine-, bromine- or methyl-substituted benzyl, or togetherwith R¹ or together with R³ represents optionally methyl- and/orethyl-substituted propane-1,3-diyl (trimethylene) or butane-1,4-diyl(tetramethylene) or an optionally fluorine-, chlorine- ormethyl-substituted benzo grouping.

R³ very particularly preferably represents hydrogen, fluorine, chlorine,bromine, in each case optionally fluorine-, chlorine-, bromine-,methoxy- or ethoxy-substituted methyl, ethyl, n- or isopropyl, oroptionally fluorine-, chlorine-, bromine- or methyl-substituted phenyl.

Z very particularly preferably represents in each case optionallysubstituted phenyl, pyridinyl, pyrimidinyl, furyl, thienyl, oxazolyl orthiazolyl, where the substituents possible in each case are inparticular selected from the following list:

-   -   nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine,        chlorine, bromine, in each case optionally cyano-, carboxyl-,        carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-, methoxy-,        ethoxy-, n- or isopropoxy-, methylthio-, ethylthio-, n- or        isopropylthio-, methylsulphinyl-, ethylsulphinyl-,        methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n-        or isopropyl, n-, iso-, s- or t-butyl, methoxy, ethoxy, n- or        isopropoxy, methoxycarbonyl, ethoxycarbonyl, n- or        isopropoxycarbonyl, methylthio, ethylthio, n- or isopropylthio,        methylsulphinyl, ethylsulphinyl, methylsulphonyl,        ethylsulphonyl, methylamino, ethylamino, n- or isopropylamino,        methylaminocarbonyl, ethylaminocarbonyl, n- or        isopropylaminocarbonyl, acetylamino, propionylamino, in each        case optionally fluorine- and/or chlorine-substituted        methylenedioxy or ethylenedioxy, dimethylamino,        dimethylaminocarbonyl or dimethylaminosulphonyl, in each case        optionally nitro-, cyano-, carboxyl-, carbamoyl-,        thiocarbamoyl-, fluorine-, chlorine-, bromine-, methyl-, ethyl-,        n- or isopropyl-, n-, iso-, s- or t-butyl-, trifluoromethyl-,        methoxy-, ethoxy-, n- or isopropoxy-, difluoromethoxy-,        trifluoromethoxy-, methylthio-, ethylthio-, n- or        isopropylthio-, difluoromethylthio-, trifluoromethylthio-,        methylsulphinyl-, ethylsulphinyl-, trifluoromethylsulphinyl-,        methylsulphonyl-, ethylsulphonyl- or        trifluoromethylsulphonyl-substituted phenyl, phenoxy,        phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,        phenylcarbonylamino, benzyl, phenylethyl, phenylmethoxy,        phenylethoxy, phenoxymethyl, phenoxyethyl, phenylmethylthio,        phenylethylthio, phenylmethylsulphinyl, phenylethylsulphinyl,        phenylmethylsulphonyl, phenylethylsulphonyl, phenylmethylamino,        phenylethylamino.

A further group of compounds according to the invention which may bementioned are the compounds in which Z represents optionally substitutedphenyl, pyridinyl, pyrimidinyl, furyl, oxazolyl or thiazolyl and mostpreferably optionally substituted phenyl, pyridinyl, pyrimidinyl orthiazolyl, where the substituents are defined as stated in the preferredranges for Z mentioned above. In this group according to the invention,only the compounds known from J. Org. Chem. 27 (1962), 181-185 are notnovel.

The novel substituted pyrimidines of the general formula (I) have strongand selective herbicidal activity.

The novel substituted pyrimidines of the general formula (I) areobtained when,

-   (a) if in the formula (I) n represents the number 0,    mercaptopyrimidines of the general formula (II)    in which-   R¹, R¹ and R³ are as defined above    are reacted with haloalkyl compounds of the general formula (III)    in which-   A and Z are as defined above and-   X represents halogen,    if appropriate in the presence of a reaction auxiliary and if    appropriate in the presence of a diluent,    or when,-   (b) if in the formula (I) n represents the number 1 or 2,    substituted pyrimidines of the general formula (Ia)    in which-   A, R¹, R²R³ and Z are as defined above    are reacted with an oxidizing agent, if appropriate in the presence    of a catalyst and if appropriate in the presence of a diluent.

Using, for example, 4,5-dimethyl-2-pyrimidinethiol and 4-fluorobenzylchloride as starting materials, the course of the reaction in theprocess (a) according to the invention can be illustrated by thefollowing formula scheme:

Using, for example,2-[(4-fluorophenyl)methylthio]-4,5-dimethylpyrimidine and hydrogenperoxide as starting materials, the course of the reaction in theprocess (b) according to the invention can be illustrated by thefollowing formula scheme:

The formula (II) provides a general definition of themercaptopyrimidines to be used as starting materials in the process (a)according to the invention for preparing compounds of the generalformula (I). In the general formula (II), R¹, R² and R³ preferably or inparticular have those meanings which have already been mentioned above,in connection with the description of the compounds of the generalformula (I) according to the invention, as being preferred or as beingparticularly preferred for R¹, R² and R³.

The starting materials of the general formula (II) are known and/or canbe prepared by processes known per se (cf. Chemiker-Zeitung 101 (1977),305-307, Chem. Ber. 110 (1977), 2872-2879, J. Chem. Soc., Perkin Trans.1, 1977, 1688-1692, J. Prakt. Chem. 321 (1979), 619-628, Heterocycles 25(1987), 393-397, Aust. J. Chem. 45 (1992), 1045-1050, DE-A-2403340,DE-A-2454728, DE-A-2455582, GB-A-2205101).

The formula (III) provides a general definition of the haloalkylcompounds further to be used as starting materials in the process (a)according to the invention for preparing compounds of the generalformula (I). In the general formula (III), A and Z preferably or inparticular have those meanings which have already been mentioned above,in connection with the description of the compounds of the generalformula (I) according to the invention, as being preferred or as beingparticularly preferred for A and Z; X preferably represents fluorine,chlorine, bromine or iodine, in particular chlorine or bromine.

The starting materials of the general formula (III) are known organicchemicals for synthesis.

The formula (Ia) provides a general definition of the substitutedpyrimidines to be used as starting materials in the process (b)according to the invention for preparing compounds of the generalformula (I). In the general formula (Ia), A, R¹, R², R³ and Z preferablyor in particular have those meanings which have already been mentionedabove, in connection with the description of the compounds of thegeneral formula (I) according to the invention, as being preferred or asbeing particularly preferred for A, R¹, R², R³ and Z.

As novel substances, the starting materials of the general formula (Ia)also form part of the subject-matter of the present application; theycan be prepared in accordance with the description of the process (a)according to the invention.

The process (b) according to the invention for preparing the compoundsof the formula (I) is carried out using an oxidizing agent. Suitableoxidizing agents are the customary chemicals suitable for oxidizingorganic sulphides (thioethers) to the corresponding sulphoxides orsulphones. Examples of suitable oxidizing agents which may be mentionedare: hydrogen peroxide (H₂O₂), performic acid, peracetic acid,perpropionic acid, perbenzoic acid and 3-chloroperbenzoic acid, and alsochlorine or hypochlorous acid and its alkali metal or alkaline earthmetal salts.

Suitable reaction auxiliaries for the process (a) according to theinvention are, in general, the customary inorganic or organic bases oracid acceptors. These preferably include alkali metal or alkaline earthmetal acetates, amides, carbonates, bicarbonates, hydrides, hydroxidesor alkoxides, such as, for example, sodium acetate, potassium acetate orcalcium acetate, lithium amide, sodium amide, potassium amide or calciumamide, sodium carbonate, potassium carbonate or calcium carbonate,sodium bicarbonate, potassium bicarbonate or calcium bicarbonate,lithium hydride, sodium hydride, potassium hydride or calcium hydride,lithium hydroxide, sodium hydroxide, potassium hydroxide or calciumhydroxide, sodium methoxide, ethoxide, n- or isopropoxide, n-, iso-, s-or t-butoxide or potassium methoxide, ethoxide, n- or isopropoxide, n-,iso-, s- or t-butoxide; furthermore also basic organic nitrogencompounds, such as, for example, trimethylamine, triethylamine,tripropylamine, tributylamine, ethyldiisopropylamine,N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine,N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-,3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, 4-dimethylaminopyridine,N-methylpiperidine, 1,4-diazabicyclo[2.2.2]octane (DABCO),1,5-diazabicyclo[4.3.0]non-5-ene (DBN), or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Further suitable reaction auxiliaries for the processes (a) and (b)according to the invention are also phase-transfer catalysts. Examplesof such catalysts which may be mentioned are:

tetrabutylammonium bromide, tetrabutylammonium chloride,tetraoctylammonium chloride, tetrabutylammonium hydrogen sulphate,methyltrioctylammonium chloride, hexadecyltrimethylammonium chloride,hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride,benzyltriethylammonium chloride, benzyltrimethylammonium hydroxide,benzyltriethylammonium hydroxide, benzyltributylammonium chloride,benzyltributylammonium bromide, tetrabutylphosphonium bromide,tetrabutylphosphonium chloride, tributylhexadecylphosphonium bromide,butyltriphenylphosphonium chloride, ethyltrioctylphosphonium bromide,tetraphenylphosphonium bromide.

The process (a) according to the invention for preparing the compoundsof the general formula (I) is preferably carried out using one or morediluents. Suitable diluents for carrying out the process (a) accordingto the invention are, in addition to water, especially inert organicsolvents. These include, in particular, aliphatic, alicyclic oraromatic, optionally halogenated hydrocarbons, such as, for example,benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether,dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethyleneglycol diethyl ether; ketones, such as acetone, butanone or methylisobutyl ketone; nitriles, such as acetonitrile, propionitrile orbutyronitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such asmethanol, ethanol, n- or isopropanol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, their mixtures with water or purewater.

The process (b) according to the invention is, if appropriate, carriedout in the presence of a catalyst. Suitable catalysts are, preferably,salts of metals of transition group IV., V. and VI. of the PeriodicTable of the Elements. Examples which may be mentioned are sodium(meta)vanadate, sodium molybdate and sodium tungstate.

The process (b) according to the invention is preferably carried outusing a diluent. Suitable diluents are, in addition to water, organicsolvents which are customary for oxidation reactions. These preferablyinclude chlorinated hydrocarbons, such as methylene chloride, ethylenechloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane,chlorobenzene and o-dichlorobenzene, alcohols, such as methanol,ethanol, propanol, isopropanol, butanol, isobutanol and sec-butanol,carboxylic acids, such as formic acid, acetic acid and propionic acid.

When carrying out the processes (a) and (b) according to the invention,the reaction temperatures can be varied within a relatively wide range.In general, the processes are carried out at temperatures between −20°C. and +150° C., preferably between 0° C. and 100° C.

The processes according to the invention are generally carried out underatmospheric pressure. However, it is also possible to carry out theprocesses according to the invention under elevated or reducedpressure—in general between 0.1 bar and 10 bar.

For carrying out the processes according to the invention, the startingmaterials are generally employed in approximately equimolar amounts.However, it is also possible to use a relatively large excess of one ofthe components. The reaction is generally carried out in a suitablediluent in the presence of a reaction auxiliary or catalyst, and thereaction mixture is generally stirred at the required temperature for anumber of hours. Work-up is carried out by customary methods (cf. thePreparation examples).

The active compounds according to the invention can be used asdefoliants, desiccants, haulm killers and, especially, as weed killers.Weeds in the broadest sense are understood to mean all plants which growin locations where they are undesired. Whether the substances accordingto the invention act as total or selective herbicides dependsessentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia,Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus,Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium,Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus,Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha,Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum,Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola,Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,Xanthium.

Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis,Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca,Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis,Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina,Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis,Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera,Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum,Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria,Sorghum.

Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena,Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale,Triticum, Zea.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The active compounds according to the invention are suitable, dependingon the concentration, for the total control of weeds, for example onindustrial terrain and rail tracks, and on paths and areas with andwithout tree plantings. Similarly, the active compounds according to theinvention can be employed for controlling weeds in perennial crops, forexample forests, decorative tree plantings, orchards, vineyards, citrusgroves, nut orchards, banana plantations, coffee plantations, teaplantations, rubber plantations, oil palm plantations, cocoaplantations, soft fruit plantings and hop fields, on lawns, turf andpastureland, and for the selective control of weeds in annual crops.

The compounds of the formula (I) according to the invention have strongherbicidal activity and a broad active spectrum when used on the soiland on above-ground parts of plants. To a certain extent they are alsosuitable for the selective control of monocotyledonous anddicotyledonous weeds in monocotyledonous and dicotyledonous crops, bothby the pre-emergence and by the post-emergence method.

At certain concentrations or application rates, the active compoundsaccording to the invention can also be employed for controlling animalpests and fungal or bacterial plant diseases. If appropriate, they canalso be used as intermediates or precursors for the synthesis of otheractive compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and inclusive of the cultivars protectable or not protectable byplant breeders' rights. Plant parts are to be understood as meaning allparts and organs of plants above and below the ground, such as shoot,leaf, flower and root, examples which may be mentioned being leaves,needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots,tubers and rhizomes. The plant parts also include harvested material,and vegetative and generative propagation material, for examplecuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulationssuch as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric materials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticmaterials such as highly-disperse silica, alumina and silicates;suitable solid carriers for granules are: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, or else synthetic granules of inorganic and organic meals,and granules of organic material such as sawdust, coconut shells, maizecobs and tobacco stalks; suitable emulsifiers and/or foam formers are:for example nonionic and anionic emulsifiers such as polyoxyethylenefatty acid esters, polyoxyethylene fatty alcohol ethers, for examplealkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,arylsulphonates, or else protein hydrolysates; suitable dispersants are:for example lignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchalizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in their formulations, can also be used as mixtures withknown herbicides and/or substances which improve the compatibility withcrop plants (“safeners”), finished formulations or tank mixes beingpossible. Also possible are mixtures with weed-killers comprising one ormore known herbicides and a safener.

Possible components for the mixtures are known herbicides, for example

acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos,asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin(-ethyl), benfuresate, bensulfuron (-methyl), bentazone, benzfendizone,benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox,bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor,butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim,carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben,chloridazon, chlorimuron (-ethyl), chlomitrofen, chlorsulfuron,chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim,clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid,clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine,cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl),2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P),diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat,diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid,diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb,ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen,ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide,flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam,fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet,flufenpyr, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn,flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl),flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol,flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen,haloxyfop (-ethoxyethyl, -P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil,isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,isoxaflutole, isoxapyrifop, ketospiradox, lactofen, lenacil, linuron,MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor,methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor,metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate,monolinuron, naproanilide, napropamide, neburon, nicosulfuron,norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron,oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin,pendralin, penoxysulam, pentoxazone, pethoxamid, phenmedipham,picolinafen, piperophos, pretilachlor, primisulfuron (-methyl),profluazol, profoxydim, prometryn, propachlor, propanil, propaquizafop,propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb,prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol,pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac,quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron,sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil,tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr,tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl),tritosulfuron.

Furthermore suitable for the mixtures are known safeners, for exampleAD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D,DKA-24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole,fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P),mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in a customary manner, for example bywatering, spraying, atomizing or broadcasting.

The active compounds according to the invention can be applied bothbefore and after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a relatively widerange. It depends essentially on the nature of the desired effect. Ingeneral, the amounts used are between 1 g and 10 kg of active compoundper hectare of soil surface, preferably between 5 g and 5 kg per ha.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and cultivars, or those obtained by conventional biologicalbreeding, such as crossing or protoplast fusion, and parts thereof, aretreated. In a further preferred embodiment, transgenic plants andcultivars obtained by genetic engineering, if appropriate in combinationwith conventional methods (Genetically Modified Organisms), and partsthereof are treated. The term “parts” or “parts of plants” or “plantparts” has been explained above.

Particularly preferably, plants of the cultivars which are in each casecommercially available or in use are treated according to the invention.Cultivars are to be understood as meaning plants having certainproperties (“traits”) and which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. They can bevarieties, bio- or genotypes.

Depending on the plant species or cultivars, their location and growthconditions (soils, climate, vegetation period, diet), the treatmentaccording to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention also in combination with other agrochemically activecompounds, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or cultivars (i.e. those obtained by geneticengineering) which are preferably treated according to the inventioninclude all plants which, in the genetic modification, received geneticmaterial which imparted particularly advantageous useful properties(“traits”) to these plants. Examples of such properties are better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch properties are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapes), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are emphasized are inparticular increased defence of the plants against insects by toxinsformed in the plants, in particular those formed in the plants by thegenetic material from Bacillus thuringiensis (for example by the genesCryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab,Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred toas “Bt plants”). Traits that are also particularly emphasized are theincreased defence of the plants to fungi, bacteria and viruses bysystemic acquired resistance (SAR), systemin, phytoalexins, elicitorsand resistance genes and correspondingly expressed proteins and toxins.Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulphonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes which impart the desired traitsin question can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylurea, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to cultivars having these genetic traits orgenetic traits still to be developed, which plants will be developedand/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the inventionwhere in addition to the effective control of the weeds, theabovementioned synergistic effects with the transgenic plants or plantcultivators occur. The preferred ranges stated above for the activecompounds or mixtures also apply to the treatment of these plants.Particular emphasis is given to the treatment of plants with thecompounds or mixtures specifically mentioned in the present text.

The preparation and the use of the active compounds according to theinvention is illustrated by the examples below.

Preparation Examples:

EXAMPLE 1

(Process (a))

4.0 g (18.5 mmol) of 4-methyl-5,6,7,8-tetrahydro-2-quinazolinethiol aredissolved in 12 ml of chloroform and, at room temperature (about 20°C.), 1.87 g (18.5 mmol) of triethylamine and 2.98 g (18.5 mmol) of4-chlorobenzyl chloride and, finally, 3.74 g (27 mmol) of triethylamineare added dropwise successively. The reaction mixture is then stirred at50° C. for 12 hours and then, at room temperature, washed with water,dried with sodium sulphate and filtered. From the filtrate, volatilecomponents are distilled off under reduced pressure. The residue isdigested with petroleum ether, and the resulting crystalline product isisolated by filtration with suction.

This gives 3.3 g (59% of theory) of2-(4-chlorobenzylthio)-4-methyl-5,6,7,8-tetrahydroquinazoline of meltingpoint 48° C.

EXAMPLE 2

(Process (b))

1.00 g (3.3 mmol) of2-(4-chlorobenzylthio)-4-methyl-5,6,7,8-tetrahydroquinazoline aredissolved in 20 ml of methylene chloride and, at 0° C., 0.80 g (3.3mmol) of m-chloroperbenzoic acid is added. The reaction mixture isstirred at 0° C. for 60 minutes and then diluted with 80 ml of methylenechloride, extracted successively with saturated aqueous sodiumbicarbonate solution and water and then dried with sodium sulphate. Fromthe filtrate, the solvent is distilled off under reduced pressure, theresidue is digested with petroleum ether and the resulting crystallineproduct is isolated by filtration with suction.

This gives 0.60 g (57% of theory) of2-(4-chlorobenzylsulphinyl)-4-methyl-5,6,7,8-tetrahydroquinazoline ofmelting point 127° C.

EXAMPLE 3

(Process (b))

1.00 g (3.3 mmol) of2-(4-chlorobenzylthio)-4-methyl-5,6,7,8-tetrahydroquinazoline aredissolved in 30 ml of chloroform and, at room temperature (about 20°C.), a spatula tip (about 0.1 mg) of ammonium molybdate, 0.68 g (13mmol) of formic acid (85% strength) and 1.24 g (13 mmol) of hydrogenperoxide (35% strength) are added successively. The reaction mixture isthen stirred at room temperature for 12 hours and then diluted with 50ml of methylene chloride, extracted successively with saturated aqueoussodium bicarbonate solution and water and then dried using sodiumsulphate. From the filtrate, the solvent is distilled off under reducedpressure, the residue is digested with petroleum ether and the resultingcrystalline product is isolated by filtration with suction.

This gives 0.47 g (42% of theory) of2-(4-chlorobenzylsulphonyl)-4-methyl-5,6,7,8-tetrahydroquinazoline ofmelting point 151° C.

Analogously to Preparation Examples 1, 2 and 3, and in accordance withthe general description of the processes according to the invention, itis also possible to prepare, for example, the compounds of the generalformula (I) listed in Table 1 below. TABLE 1 (I)

Examples of compounds of the formula (I) Ex. No. n A R¹ R² R³ Z Meltingpoint (° C.) 4 2 CH₂ CH₃ R² + R³: (CH₂)₃

179  5 0 CH₂ CH₃ R² + R³: (CH₂)₃

35 6 0 CH₂ H C₂H₅ CH₃

(amorphous) 7 0 CH₂ H C₂H₅ CH₃

47 8 0 CH₂ H C₂H₅ CH₃

32 9 0 CH₂ H C₂H₅ CH₃

47 10 0 CH₂ H C₂H₅ CH₃

(amorphous) 11 0 CH₂ CH₃ CH₃ CH₃

103  12 0 CH₂ CH₃ CH₃ CH₃

66 13 0 CH₂ CH₃ CH₃ CH₃

65 14 0 CH₂ CH₃ CH₃ CH₃

66 15 1 CH₂ H C₂H₅ CH₃

(amorphous) 16 1 CH₂ H C₂H₅ CH₃

45 17 1 CH₂ H C₂H₅ CH₃

90 18 1 CH₂ H C₂H₅ CH₃

59 19 1 CH₂ CH₃ CH₃ CH₃

99 20 1 CH₂ CH₃ CH₃ CH₃

113  21 1 CH₂ CH₃ CH₃ CH₃

43 22 1 CH₂ CH₃ CH₃ CH₃

164  23 1 CH₂ H C₃H₇-n H

(amorphous) 24 1 CH₂ H C₃H₇-n H

(amorphous) 25 1 CH₂ H C₃H₇-n H

(amorphous) 26 1 CH₂ H C₃H₇-n H

54 27 0 CH₂ Cl

Cl

153 28 0 CH₂ H C₃H₇-n H

(amorphous) 29 1 CH₂ H C₂H₅ CH₃

47 30 2 CH₂ H C₂H₅ CH₃

76 31 0 CH₂ H C₃H₇-n H

(amorphous) 32 0 CH₂ H C₃H₇-n H

65 33 0 CH₂ H C₃H₇-n H

(amorphous) 34 2 CH₂ H C₂H₅ CH₃

90 35 2 CH₂ H C₂H₅ CH₃

103  36 2 CH₂ H C₂H₅ CH₃

75 37 2 CH₂ H C₂H₅ CH₃

108  38 2 CH₂ CH₃ CH₃ CH₃

158  39 2 CH₂ CH₃ CH₃ CH₃

146  40 2 CH₂ CH₃ CH₃ CH₃

108  41 2 CH₂ CH₃ CH₃ CH₃

118  42 2 CH₂ H C₃H₇-n H

(amorphous) 43 2 CH₂ H C₃H₇-n H

(amorphous) 44 2 CH₂ H C₃H₇-n H

96 45 2 CH₂ H C₃H₇-n H

81 46 0 CH₂ CH₃ C₂H₅ CH₃

60 47 0 CH₂ CH₃ C₃H₇-n CH₃

30 48 0 CH₂ CH₃ C₄H₉-n CH₃

31 49 1 CH₂ CH₃ C₃H₇-n CH₃

143  50 2 CH₂ CH₃ C₃H₇-n CH₃

92 51 2 CH₂ CH₃ C₄H₉-n CH₃

71 52 1 CH₂ CH₃ C₂H₅ CH₃

109  53 2 CH₂ CH₃ C₂H₅ CH₃

115  54 1 CH₂ CH₃ C₄H₉-n CH₃

76 55 1 CH₂ CH₃ R² + R³: (CH₂)₃

170  56 1 CH₂ CH₃ CH₃ CH₃

98 57 1 CH₂ CH₃ CH₃ CH₃

87 58 1 CH₂ CH₃ CH₃ CH₃

180  59 2 CH₂ CH₃ CH₃ CH₃

146  60 2 CH₂ CH₃ CH₃ CH₃

162  61 0 CH(CH₃) CH₃ CH₃ CH₃

123 (racemate) 62 0 CH₂ CH₃ CH₃ CH₃

80 63 0 CH₂ CH₃ CH₃ CH₃

148  64 0 CH₂ CH₃ CH₃ CH₃

110  65 1 CH(CH₃) CH₃ CH₃ CH₃

123 (racemate) 66 2 CH(CH₃) CH₃ CH₃ CH₃

123 (racemate) 67 1 CH₂ CH₃ CH₃ CH₃

153  68 2 CH₂ CH₃ CH₃ CH₃

(amorphous) 69 2 CH₂ CH₃ CH₃ CH₃

113  70 2 CH₂ CH₃ CH₃ CH₃

150  71 2 CH₂ CH₃ CH₃ CH₃

107  72 2 CH₂ CH₃ CH₃ CH₃

103  73 1 CH₂ CH₃ CH₃ CH₃

103  74 0 CH₂ CH₃ CH₃ CH₃

62 75 0 CH₂ CH₃ CH₃ CH₃

65 76 0 CH₂ CH₃ CH₃ CH₃

112  77 0 CH₂ CH₃ CH₃ CH₃

126  78 0 CH₂ CH₃ CH₃ CH₃

91 79 0 CH₂ CH₃ CH₃ CH₃

60 80 0 CH₂ CH₃ CH₃ CH₃

35 81 0 CH₂ CH₃ CH₃ CH₃

65 82 1 CH₂ CH₃ CH₃ CH₃

102  83 0 CH₂ CH₃ CH₃ CH₃

80 84 2 CH₂ CH₃ CH₃ CH₃

148  85 1 CH₂ CH₃ CH₃ CH₃

134  86 1 CH₂ CH₃ CH₃ CH₃

130  87 0 CH₂ CH₃ CH₃ CH₃

78 88 1 CH₂ CH₃ CH₃ CH₃

147  89 1 CH₂ CH₃ CH₃ CH₃

149  90 1 CH₂ CH₃ CH₃ CH₃

101  91 0 CH₂ CH₃ CH₃ CH₃

52 92 0 CH₂ CH₃ CH₃ CH₃

98 93 2 CH₂ CH₃ CH₃ CH₃

134  94 0 CH₂ CH₃ CH₃ CH₃

77 95 0 CH₂ CH₃ CH₃ CH₃

111  96 1 CH₂ CH₃ CH₃ CH₃

126  97 1 CH₂ CH₃ CH₃ CH₃

166  98 0 CH₂ CH₃ CH₃ CH₃

83 99 2 CH₂ CH₃ CH₃ CH₃

95 100 2 CH₂ CH₃ CH₃ CH₃

90 101 2 CH₂ CH₃ CH₃ CH₃

108  102 2 CH₂ CH₃ CH₃ CH₃

190  103 1 CH₂ CH₃ CH₃ CH₃

190  104 2 CH₂ CH₃ CH₃ CH₃

203  105 0 CH₂ CH₃ CH₃ CH₃

118  106 0 CH₂ CH₃ CH₃ CH₃

48 107 2 CH₂ CH₃ CH₃ CH₃

128  108 2 CH₂ CH₃ CH₃ CH₃

116  109 2 CH₂ CH₃ CH₃ CH₃

183  110 0 CH₂ CH₃ C₂H₅ CH₃

94 111 0 CH₂ CH₃ C₃H₇-n CH₃

80 112 0 CH₂ CH₃ C₄H₉-n CH₃

80 113 0 CH₂ CH₃ R² + R³: (CH₂)₃

105  114 0 CH₂ CH₃ R² + R³: (CH₂)₄

64 115 2 CH₂ CH₃ CH₃ CH₃

153  116 1 CH₂ CH₃ CH₃ CH₃

154  117 1 CH₂ CH₃ CH₃ CH₃

181  118 2 CH₂ CH₃ CH₃ CH₃

134  119 1 CH₂ CH₃ CH₃ CH₃

117  120 1 CH₂ CH₃ CH₃ CH₃

104  121 2 CH₂ CH₃ R² + R³: (CH₂)₃

166  122 2 CH₂ CH₃ R² + R³: (CH₂)₄

148  123 1 CH₂ CH₃ CH₃ CH₃

171  124 1 CH₂ CH₃ R² + R³: (CH₂)₃

166  125 1 CH₂ CH₃ R² + R³: (CH₂)₄

143  126 2 CH₂ CH₃ C₃H₇-n CH₃

117  127 2 CH₂ CH₃ C₄H₉-n CH₃

84 128 2 CH₂ CH₃ C₂H₅ CH₃

105  129 2 CH₂ CH₃ CH₃ CH₃

103  130 1 CH₂ CH₃ C₂H₅ CH₃

107  131 1 CH₂ CH₃ C₄H₉-n CH₃

89 132 1 CH₂ CH₃ CH₃ CH₃

154  133 1 CH₂ CH₃ C₃H₇-n CH₃

91 134 0 CH₂ CH₃ CH₃ CH₃

209  136 0 CH₂ CH₃ CH₃ CH₃

105  137 0 CH₂ CH₃ CH₃ CH₃

64 138 0 CH₂ CH₃ CH₃ CH₃

67 139 0 CH₂ CH₃ CH₃ CH₃

75 140 2 CH₂ CH₃ CH₃ CH₃

98 141 1 CH₂ CH₃ CH₃ CH₃

110  142 1 CH₂ CH₃ CH₃ CH₃

(oil) 144 2 CH₂ CH₃ CH₃ CH₃

76 145 2 CH₂ CH₃ CH₃ CH₃

(oil) 146 1 CH₂ CH₃ CH₃ CH₃

161  147 0 CH₂CH₂ CH₃ CH₃ CH₃

224  148 0 CH₂ CH₃ CH₃ CH₃

(oil) 149 0 CH₂ C₆H₅

93 150 0 CH₂ C₆H₅

92 151 2 CH₂ CH₃ CH₃ CH₃

176  152 1 CH₂ CH₃ CH₃ CH₃

(oil) 153 2 CH₂ CH₃ CH₃ CH₃

88 154 0 CH₂ CH₃ CH₃ CH₃

72 155 2 CH₂CH₂ CH₃ CH₃ CH₃

118  156 1 CH₂CH₂ CH₃ CH₃ CH₃

(oil) 157 0 CH₂ CH₃ CH₃ CH₃

59 158 2 CH₂ CH₃ CH₃ CH₃

(oil) 159 2 CH₂ C₆H₅

105  160 1 CH₂ C₆H₅

(oil) 161 1 CH₂ CH₃ CH₃ CH₃

(oil) 162 1 CH₂ C₆H₅

129  163 2 CH₂ C₆H₅

197  164 2 CH₂ CH₃ CH₃ CH₃

143  165 1 CH₂ CH₃ CH₃ CH₃

(oil) 166 2 CH₂ CH₃ CH₃ CH₃

167 2 (CH₂)₃ CH₃ CH₃ CH₃

81 168 0 (CH₂)₃ CH₃ CH₃ CH₃

65 169 1 (CH₂)₃ CH₃ CH₃ CH₃

72 170 1 CH₂ H CH₃ CH₃

104  171 2 CH₂ H CH₃ CH₃

78Use Examples:

EXAMPLE A

Post-Emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants of a height of 5-15 cm are sprayed with the preparation ofactive compound such that the particular amounts of active compounddesired are applied per unit area. The concentration of the spray liquoris chosen such that the particular amounts of active compound desiredare applied in 1000 l of water/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

In this test, for example, the compounds of Preparation Examples 4, 22,55, 85 and 88 exhibit strong activity against weeds, and some of themare tolerated well by crop plants such as, for example, maize.

EXAMPLE B

Pre-Emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil. After 24 hours, thesoil is sprayed with the preparation of active compounds such that theparticular amount of active compound desired is applied per unit area.The concentration of active compound in the spray liquor is chosen suchthat the particular amount of active compound desired is applied in 1000litres of water per hectare.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

-   -   0%=no effect (like untreated control)    -   100%=total destruction

In this test, for example, the compounds of the Preparation Examples 4,20, 22, 41, 55, 58, 60, 85, 88, 93, 97 and 166 exhibit strong activityagainst weeds, and some of them are tolerated well by crop plants, suchas, for example, maize. TABLE A1 Post-emergence-Test/greenhouse Compoundof Preparation application Example No. rate (g a.i./ha) maize SorghumAmaranthus Polygonum Veronica (4) 2000 0 80 100 80 80

TABLE A2 Post-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Setaria Abutilon AmaranthusGalium Ipomoea Sinapis (22) 2000 95 100 100 95 90 — (55) 2000 80  95 10080 — 80 (85) 2000 90 —  90 95 — 70

TABLE A3 Post-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) maize Setaria AbutilonAmaranthus Galium Sinapis (88) 1000 10 90 80 100 90 80

TABLE B1 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Setaria Amaranthus PolygonumVeronica Viola (4) 4000 70 100 95 90 80

TABLE B2 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) maize Setaria Amaranthus GaliumIpomoea Sinapis (20) 2000 0 95 90 90 80 — (22) 2000 0 100 100 90 80 80

TABLE B3 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) maize Setaria AbutilonAmaranthus Galium (55) 1000 10 90 70 100 80

TABLE B4 Pre-emergence-Test/greenhouse Compound of Preparationapplication Avena Example No. rate (g a.i./ha) Alopecurus fatua SetariaAmaranthus Galium (41) 2000 90 80 100 100 80

TABLE B5 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Alopecurus Setaria AmaranthusGalium Ipomoea (166) 2000 70  95 100 95 —  (60) 2000 80 100 100 90 70

TABLE B6 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Setaria Abutilon AmaranthusGalium Ipomoea (58) 2000 90 100 100 90 80

TABLE B7 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Alopecurus Setaria AbutilonAmaranthus Galium (85) 2000 80 100 100 100 100

TABLE B8 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Alopecurus Setaria AbutilonAmaranthus Galium Sinapis (88) 2000 80 100 80 100 80 90

TABLE B9 Pre-emergence-Test/greenhouse Compound of Preparationapplication Example No. rate (g a.i./ha) Avena fatua Setaria AmaranthusGalium Ipomoea (97) 2000 80 95  90 80 — (93) 2000 80 80 100 90 95

1-9. (Canceled).
 10. A compound of formula (I)

in which n represents the number 0, 1, or 2, A represents straight-chainor branched alkanediyl having 1 to 6 carbon atoms, R¹ representshydrogen, halogen, optionally halogen- or C₁-C₄-alkoxy-substituted alkylhaving 1 to 6 carbon atoms, or optionally halogen- orC₁-C₄-alkyl-substituted phenyl, R² represents optionally halogen- orC₁-C₄-alkoxy-substituted alkyl having 1 to 6 carbon atoms; representsoptionally halogen- or C₁-C₄-alkyl-substituted cycloalkyl having 3 to 8carbon atoms; or represents optionally halogen- orC₁-C₄-alkyl-substituted phenyl-C₁-C₄-alkyl, or together with R¹ ortogether with R³ represents optionally C₁-C₄-alkyl-substitutedalkanediyl having 3 to 5 carbon atoms or an optionally halogen- orC₁-C₄-alkyl-substituted benzo group, R³ represents hydrogen, halogen,optionally halogen- or C₁-C₄-alkoxy-substituted alkyl having 1 to 6carbon atoms, or optionally halogen- or C₁-C₄-alkyl-substituted phenyl,and Z represents optionally substituted phenyl, naphthyl, pyridinyl,pyrimidinyl, furyl, thienyl, oxazolyl, or thiazolyl, wherein thesubstituents are nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, orhalogen; optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-,halogen-, C₁-C₄-alkoxy-, C₁-C₄-alkylthio-, C₁-C₄-alkylsulphinyl-, orC₁-C₄-alkylsulphonyl-substituted alkyl, alkoxy, alkoxycarbonyl,alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino,alkylaminocarbonyl, or alkylcarbonylamino having in each case 1 to 6carbon atoms in the alkyl groups; optionally halogen-substitutedalkylenedioxy having 1 or 2 carbon atoms; dialkylamino,dialkylaminocarbonyl, or dialkylaminosulphonyl having in each case 1 to4 carbon atoms in the alkyl groups; or optionally nitro-, cyano-,carboxyl-, carbamoyl-, thiocarbamoyl-, halogen-, C₁-C₄-alkyl-,C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,C₁-C₄-haloalkylthio-, C₁-C₄-alkylsulphinyl-, C₁-C₄-haloalkylsulphinyl-,C₁-C₄-alkylsulphonyl-, or C₁-C₄-haloalkylsulphonyl-substituted phenyl,phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,phenylcarbonylamino, phenyl-C₁-C₄-alkyl, phenyl-C₁-C₄-alkoxy,phenoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkylthio,phenyl-C₁-C₄-alkylsulphinyl, phenyl-C₁-C₄-alkylsulphonyl, orphenyl-C₁-C₄-alkylamino, except for the compounds2-benzylthio-4-chloro-5-methylpyrimidine,4-chloro-2-(2,4-dichlorobenzylthio)-5-methylpyrimidine,4-chloro-2-(chlorobenzylthio)-5-methylpyrimidine and4-chloro-2-(4-chlorobenzylthio)-5-methylpyrimidine,4,6-dichloro-5-methyl-2-(naphthalen-2-ylmethylthio)pyrimidine,5-methyl-2-[(1-methyl-5-nitro-1H-imidazol-2-yl)methylthio]pyrimidine,2-(thien-2-ylmethylsulphonyl)-5-trifluoromethylpyrimidine,2-phenylmethylthio-5-trifluoromethylpyrimidine,2-(thien-2-ylmethylthio)-5-trifluoromethylpyrimidine,2-phenylmethylsulphonyl-5-trifluoromethylpyrimidine, and2-(thien-2-ylmethylsulphinyl)-5-trifluoromethylpyrimidine.
 11. Acompound according to claim 10 in which n represents the number 0, 1, or2, A represents straight-chain or branched alkanediyl having 1 to 4carbon atoms, R¹ represents hydrogen, halogen, optionally halogen- orC₁-C₄-alkoxy-substituted alkyl having 1 to 4 carbon atoms, or optionallyhalogen- or C₁-C₄-alkyl-substituted phenyl, R² represents optionallyhalogen- or C₁-C₄-alkoxy-substituted alkyl having 1 to 5 carbon atoms;represents optionally halogen- or C₁-C₃-alkyl-substituted cycloalkylhaving 3 to 7 carbon atoms; or represents optionally halogen- orC₁-C₄-alkyl-substituted phenyl-C₁-C₄-alkyl; or R² together with R¹ or R²together with R³ represents optionally C₁-C₃-alkyl-substitutedalkanediyl having 3 to 5 carbon atoms or an optionally halogen- orC₁-C₃-alkyl-substituted benzo group, R³ represents hydrogen, halogen,optionally halogen- or C₁-C₄-alkoxy-substituted alkyl having 1 to 4carbon atoms, or optionally halogen- or C₁-C₄-alkyl-substituted phenyl,and Z represents optionally substituted phenyl, naphthyl, pyridinyl,pyrimidinyl, furyl, thienyl, oxazolyl, or thiazolyl, wherein thesubstituents are nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, orhalogen; optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-,halogen-, C₁-C₄-alkoxy-, C₁-C₄-alkylthio-, C₁-C₄-alkylsulphinyl-, orC₁-C₄-alkylsulphonyl-substituted alkyl, alkoxy, alkoxycarbonyl,alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino,alkylaminocarbonyl, or alkylcarbonylamino having in each case 1 to 5carbon atoms in the alkyl groups; optionally halogen-substitutedalkylenedioxy having 1 or 2 carbon atoms; dialkylamino,dialkylaminocarbonyl, or dialkylaminosulphonyl having in each case 1 to3 carbon atoms in the alkyl groups; or optionally nitro-, cyano-,carboxyl-, carbamoyl-, thiocarbamoyl-, halogen-, C₁-C₄-alkyl-,C₁-C₄-haloalkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,C₁-C₄-haloalkylthio-, C₁-C₄-alkylsulphinyl-, C₁-C₄-haloalkylsulphinyl-,C₁-C₄-alkylsulphonyl-, or C₁-C₄-haloalkylsulphonyl-substituted phenyl,phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,phenylcarbonylamino, phenyl-C₁-C₄-alkyl, phenyl-C₁-C₄-alkoxy,phenoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkylthio,phenyl-C₁-C₄-alkylsulphinyl, phenyl-C₁-C₄-alkylsulphonyl, orphenyl-C₁-C₄-alkylamino.
 12. A compound according to claim 10 in which Arepresents methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl(dimethylene), propane-1,1-diyl (propylidene), propane-1,2-diyl, orpropane-1,3-diyl (trimethylene), R¹ represents hydrogen, fluorine,chlorine, bromine, or iodine; represents optionally fluorine-,chlorine-, bromine-, methoxy-, ethoxy-, or n- or isopropoxy-substitutedmethyl, ethyl, n- or isopropyl, n-, iso-, s-, or t-butyl; or representsoptionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- orisopropyl-, or n-, iso-, s-, or t-butyl-substituted phenyl, R²represents optionally fluorine-, chlorine-, bromine-, methoxy-, ethoxy-,or n- or isopropoxy-substituted methyl, ethyl, n- or isopropyl, n-,iso-, s-, or t-butyl; represents optionally fluorine-, chlorine-,methyl-, or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, orcyclohexyl; or represents optionally fluorine-, chlorine-, bromine-,methyl-, ethyl-, n- or isopropyl, or n-, iso-, s-, ort-butyl-substituted benzyl or phenylethyl; or R² together with R¹ or R²together with R³ represents optionally methyl- and/or ethyl-substitutedpropane-1,3-diyl (trimethylene) or butane-1,4-diyl (tetramethylene) oran optionally fluorine-, chlorine-, or methyl-substituted benzo group,R³ represents hydrogen, fluorine, chlorine, bromine, or iodine;represents optionally fluorine-, chlorine-, bromine-, methoxy-, ethoxy-,or n- or isopropoxy-substituted methyl, ethyl, n- or isopropyl, or n-,iso-, s-, or t-butyl; or represents optionally fluorine-, chlorine-,bromine-, methyl-, ethyl-, n- or isopropyl-, or n-, iso-, s-, ort-butyl-substituted phenyl, and Z represents optionally substitutedphenyl, naphthyl, pyridinyl, pyrimidinyl, furyl, thienyl, oxazolyl, orthiazolyl, wherein the substituents are nitro, cyano, carboxyl,carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or iodine;optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-,chlorine-, methoxy-, ethoxy-, n- or isopropoxy-, methylthio-,ethylthio-, n- or isopropylthio-, methylsulphinyl-, ethylsulphinyl-,methylsulphonyl-, or ethylsulphonyl-substituted methyl, ethyl, n- orisopropyl, n-, iso-, s-, or t-butyl, methoxy, ethoxy, n- or isopropoxy,n-, iso-, s-, or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- orisopropoxycarbonyl, methylthio, ethylthio, n- or isopropylthio, n-,iso-, s-, or t-butylthio, methylsulphinyl, ethylsulphinyl, n- orisopropyl-sulphinyl, methylsulphonyl, ethylsulphonyl, methylamino,ethylamino, n- or isopropylamino, n-, iso-, s-, or t-butylamino,methylaminocarbonyl, ethylaminocarbonyl, n- or isopropylaminocarbonyl,acetylamino, propionylamino, or n- or isobutyroylamino; optionallyfluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy;dimethylamino, diethylamino, dimethylaminocarbonyl, ordimethylaminosulphonyl; or optionally nitro-, cyano-, carboxyl-,carbamoyl-, thiocarbamoyl-, fluorine-, chlorine-, bromine-, methyl-,ethyl-, n- or isopropyl-, n-, iso-, s-, or t-butyl-, trifluoromethyl-,methoxy-, ethoxy-, n- or isopropoxy-, difluoromethoxy-,trifluoromethoxy-, methylthio-, ethylthio-, n- or isopropylthio-,difluoromethylthio-, trifluoropmethylthio-, methylsulphinyl-,ethylsulphinyl-, trifluoromethylsulphinyl-, methylsulphonyl-,ethylsulphonyl-, or trifluoromethylsulphonyl-substituted phenyl,phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, phenylamino,phenylcarbonylamino, benzyl, phenylethyl, phenylmethoxy, phenylethoxy,phenoxymethyl, phenoxyethyl, phenylmethylthio, phenylethylthio,phenylmethylsulphinyl, phenylethylsulphinyl, phenylmethylsulphonyl,phenylethylsulphonyl, phenylmethylamino, or phenylethylamino.
 13. Acompound according to claim 10 in which A represents methylene,ethane-1,1-diyl (ethylidene), or ethane-1,2-diyl (dimethylene), R¹represents hydrogen, fluorine, chlorine, or bromine; representsoptionally fluorine-, chlorine-, bromine-, methoxy-, orethoxy-substituted methyl, ethyl, n- or isopropyl; or representsoptionally fluorine-, chlorine-, bromine-, or methyl-substituted phenyl,R² represents optionally fluorine-, chlorine-, bromine-, methoxy-, orethoxy-substituted methyl, ethyl, n- or isopropyl, or n-, iso-, ors-butyl; or represents optionally fluorine-, chlorine-, bromine-, ormethyl-substituted benzyl; or R² together with R¹ or R² together with R³represents optionally methyl- and/or ethyl-substituted propane-1,3-diyl(trimethylene) or butane-1,4-diyl (tetramethylene) or an optionallyfluorine-, chlorine-, or methyl-substituted benzo group, R³ representshydrogen, fluorine, chlorine, or bromine; represents optionally-fluorine-, chlorine-, bromine-, methoxy-, or ethoxy-substituted methyl,ethyl, or n- or isopropyl; or represents optionally fluorine-,chlorine-, bromine-, or methyl-substituted phenyl, and Z representsoptionally substituted phenyl, pyridinyl, pyrimidinyl, furyl, thienyl,oxazolyl, or thiazolyl, wherein the substituents are nitro, cyano,carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, or bromine;optionally cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, fluorine-,chlorine-, methoxy-, ethoxy-, n- or isopropoxy-, methylthio-,ethylthio-, n- or isopropylthio-, methylsulphinyl-, ethylsulphonyl-,methylsulphonyl-, or ethylsulphonyl-substituted methyl, ethyl, n- orisopropyl, n-, iso-, s-, or t-butyl, methoxy, ethoxy, n- or isopropoxy,methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, methylthio,ethylthio, n- or isopropylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl, ethylsulphonyl, methylamino, ethylamino, n- orisopropylamino, methylaminocarbonyl, ethylaminocarbonyl, n- orisopropylaminocarbonyl, acetylamino, or propionylamino; optionallyfluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy;dimethylamino, dimethylaminocarbonyl, or dimethylaminosulphonyl; oroptionally nitro-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-,fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or isopropyl-, n-,iso-, s-, or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- orisopropoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-,ethylthio-, n- or isopropylthio-, difluoromethylthio-,trifluoromethylthio-, methylsulphinyl-, ethylsulphinyl-,trifluoromethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, ortrifluoromethylsulphonyl-substituted phenyl, phenoxy, phenylthio,phenylsulphinyl, phenylsulphonyl, phenylamino, phenylcarbonylamino,benzyl, phenylethyl, phenylmethoxy, phenylethoxy, phenoxymethyl,phenoxyethyl, phenylmethylthio, phenylethylthio, phenylmethylsulphinyl,phenylethylsulphinyl, phenylmethylsulphonyl, phenylethylsulphonyl,phenylmethylamino, or phenylethylamino.
 14. A compound according toclaim 10 in which Z represents optionally substituted phenyl, pyridinyl,pyrimidinyl, or thiazolyl, where the substituents of Z are as defined inclaim
 10. 15. A process for preparing a compound according to claim 10comprising (a) for compounds of formula (I) in which n represents thenumber 0, reacting a mercaptopyrimidine of formula (II)

 in which R¹, R², and R³ are as defined for formula (I) in claim 10,with a haloalkyl compound of formula (III)

 in which A and Z are as defined for formula (I) in claim 10, and Xrepresents halogen, optionally in the presence of a reaction auxiliaryand optionally in the presence of a diluent, or (b) for compounds offormula (I) in which n represents the number 1 or 2, reacting asubstituted pyrimidine of formula (Ia)

 in which A, R¹, R², R³ and Z are as defined for formula (I) in claim10, with an oxidizing agent, optionally in the presence of a catalystand optionally in the presence of a diluent.
 16. A herbicidalcomposition comprising one or more compounds according to claim 10 or acompound excluded in claim 10 and one or more extenders and/orsurfactants.
 17. A method for controlling unwanted vegetation comprisingallowing one or more compounds according to claim 10 or a compoundexcluded in claim 10 to act on unwanted plants and/or their habitat.